Production and treatment of textile and other materials made of or containing cellulose



Patented Dec. 31, 1935 PRODUCTION AND TREATMENT OF TEX- TILE AND OTHER IVIATEEIALS MADE OF OR CONTAINING CELLULGSE Henry Dreyfus, London, England No Drawing. Application May 8, 1930, Serial No.

450,872. In Great Britain May 31, 1929 9 Claims.

This invention relates to the production of artificial filaments, threads, ribbons, films and the like from solutions containing cellulose and also relates to the treatment of artificial or natural filaments, threads, ribbons, films, fabrics or other materials made of or containing cellulose.

In the manufacture of filaments and the like from viscose with a view to the production of products of improved tensile strength, the use of coagulating baths containing strong mineral acids, for example sulphuric acid, and for unripened viscose made from unripened alkali cellulose the use of coagulating baths containing acid esters of mineral acids, for example ethyl sulphuric acid, have been suggested. Furthermore for the same purpose it has been proposed to employ the strong mineral acids in a bath through which the filaments are passed after emergence from an ordinary coagulating-bath. The use of strongly acidic baths presents many obvious disadvantages.

I have now found that disadvantages attending the use of such strong acids may be avoided, and products having very desirable properties obtained, by employing sulphonic acids or similar organo-mineral acids. I have further found that the properties of cellulosic materials in general,

natural or artificial, may be improved by a treat-- ment with organo-mineral acids.

, The present invention accordingly comprises broadly the treatment of cellulosic materials, for example filaments, threads, ribbons, films or the like, with organo-mineral acids, for example sulphonic acids, or with strong aqueous or other solutions thereof. The term organo-mineral acids is used as denoting the derivatives theoretically obtainable by replacing one or more hydroxy groups of a dior poly-basic mineral acid with one or more aryl, alkyl or aralkyl or other organic radicles, one or more hydroxy groups still remaining therein.

The treatment in general results in an improved strength and/or elasticity of the material and/or in a modification of the surface thereof, and particularly a modification in lustre.

The treatment with the sulphonic acids or other organo-mineral acids may be efiected in any desired manner. In the case of treating finished materials made of or containing natural cellulosic fibres such as cotton, or of artificial cellulosic fibres, for example viscose, nitrocellulose or cuprammonium artificial silks, the treatment may be applied to the materials under tension or so as to allow the materials to shrink. Artificial filaments, threads, ribbons or the like may further be treated by means of the sulphonic acids or other organo-mineral acids continuously with their production. For example viscose filaments on emergence from the coagulating bath may be carried directly into a second bath containing one or more organo-mineral acids.

The present invention however is productive of the most useful results when the organo-mineral acids are employed directly as coagulating baths for viscose, and especially for viscose made from unripened alkali cellulose or from alkali cellulose which has been ripened for a relatively short time. Preferably the viscose is itself unripened or given only a comparatively short ripening.

As previously indicated the treatment with the sulphonic acids or other organo-mineral acids may be applied to the material under tension, but I find that particularly valuable results are obtainable if the tension be such as to cause a stretch in the materials or if a stretch be applied to the materials immediately after the treatment with the acids.

Whatever type of material is treated and whatever method is employed the materials after treatment are preferably allowed to remain in contact with the sulphonic acids or other organimineral acids for a short time, after which they may if necessary be washed to remove the acids and avoid any destruction consequent upon prolonged contact of the materials therewith. For example they may be washed with water alone or with water containing alkali or other base.

The acids or their concentrations should be so chosen or adjusted as to avoid any substantial deleterious effect upon the materials under treatment. The acids may be applied at atmospheric temperature or at temperatures below atmospheric, for example to 10 C., or at temperatures somewhat above atmospheric temperature.

If necessary or desirable, additions may be made to the baths containing the acids, for example an addition of glycerin, glucose, or other sugars, sodium sulphate or other salts, alcohols or sulphonated oils. Such additions preferably have no action on the acid constituents of the baths.

As examples of suitable acids the following may be mentioned: methyl sulphonic acid, ethylene sulphonic acid, propyl 1.2 or 1.3 di-sulphonic acid, sulphoacetic acid, sulpho-succinic acid, ethanol sulphonic acid, benzyl sulphonic acid, benzene. sulphonic acid, phenol sulphonic acids, phenol di-sulphonic acids, sulpho-salicylic acid, sulphophthalic acid, naphthalene sulphonic acids, naphthol sulphonic acids, methyl phosphinic acid, nitro-phenyl-phosphinic acid, etc.

I find that the best results are obtained with the aliphatic sulphonic acids. The aliphatic sulphonic acids or other sulphonic acids or other organo-mineral acids may be applied in concentrated aqueous solution, for example solutions containing 30 to 50% or preferably still higher concentrations where these are obtainable, or in solution in organic solvents or in mixed aqueous organic solvents.

The following examples show the best methods known to me for carrying the invention into effect but they are not to be considered as limiting the invention in any way:

Example 1 A viscose obtained from an unmatured alkali cellulose or from an alkali cellulose which has been matured for a relatively short time, for example up to 20-30 hours, and in which the viscose has been allowed to age for about '70 to 80 hours at 17 C., is spun through a nozzle having spinning apertures of .08 millimetres diameter into a 60% aqueous solution of sulpho-acetic acid maintained at about 10 C. the length of immersion of the filaments being 20 inches, and the yarn being carried out of the coagulating bath and being wound on a bobbin rotating at a peripheral speed of about 30 meters per minute, the bobbin being arranged to run in Water or being sprayed with water. The threads may be further washed and dried as desired.

Example 2 A viscose prepared as in Example 1 is spun into a coaguating bath consisting of an aqueous solution containing 10% of sulphuric acid, 1% of ammonium sulphate, 15% of sodium sulphate and 10% of glucose. The formed filaments are carried round a feed roller and thence into a bath consisting of a 60% aqueous solution of sulphoacetic acid, after which they are'further treated as in Example 1.

In a similar manner finished dried viscose fi1aments or threads may be treated with the sulphonic acids, and furthermore natural cellulosic fibres, for example cotton, may likewise be treated. Again other sulphonic acids or other organo-mineral acids for example those listed above, may be used for the treatment.

The term solutions of cellulosic material, as used hereinafter in the claims, is to be understood as meaning a solution of cellulose or of a derivative thereof which is unstable and capable of ready regeneration, e. g. cellulose xanthate, and the term does not include solutions of organic esters or ethers of cellulose which are relatively stable.

What I claim and desire to secure by Letters 5 Patent is:

1. Process for the manufacture of artificial materials comprising treating materials of the regenerated cellulosic type with sulphonic acids of concentration at least 60% in the absence of mineral acids.

2. Process for the production of artificial materials of the regenerated cellulosic type comprising extruding solutions of cellulosic material into sulphonic acids of concentration at least 60% in the absence of mineral acids.

3. Process for the manufacture of artificial materials comprising treating materials of the regenerated cellulosic type with sulphonic acids of concentration at least 60% in the absence of mineral acids, and stretching the materials.

4. Process for the production of artificial materials of the regenerated cellulosic type comprising extruding solutions of cellulosic material into sulphonic acids of concentration at least 60% in the absence of mineral acids, and stretching the materials.

5. Process for the manufacture of artificial materials comprising treating materials of the regenerated cellulosic type with aliphatic sulphonic acids of concentration at least 60% in the absence of mineral acids. 6. Process for the production of artificial materials of the regenerated cellulosic type comprising extruding solutions of cellulosic material into aliphatic sulphonic acids of concentration at least 60% in the absence of mineral acids.

7. Process for the manufacture of artificial materials which comprises treating materials of the regenerated cellulosic type with sulphacetic acid of concentration at least 60% in the absence of mineral acids.

8. Process for the manufacture of artificial materials which comprises treating materials of the regenerated cellulosic type with sulphacetic acid of concentration at least in the ab sence of mineral acids, and stretching the materials.

9. Process for the production of artificial ma- 60 terials of the regenerated cellulosic type comprising extruding solutions of cellulosic material into sulphacetic acid of concentration at least 60% in the absence of mineral acids, and stretching the materials.

HENRY DREYFUS. 

